Composite membranes for fluid separations

ABSTRACT

A method for designing and making composite membranes having a microporous support membrane coated with a permselective layer. The method involves calculating the minimum thickness of the permselective layer such that the selectivity of the composite membrane is close to the intrinsic selectivity of the permselective layer. The invention also provides high performance membranes with optimized properties.

This invention was made with Government support under Contract NumberDE-ACAc07-831D12379, awarded by the Department of Energy. The Governmenthas certain rights in this invention.

FIELD OF THE INVENTION

The present invention pertains to the field of separation membranes.More particularly, the invention concerns the optimization of theperformance of composite membranes having a microporous support layerand a relatively thin selective layer. The membranes can be used in gasseparation, vapor separation or pervaporation.

BACKGROUND OF THE INVENTION

Pervaporation is a low-pressure membrane process that can be used toseparate components of differing volatilities from solutions. Themembranes used are selectively permeable (permselective) to onecomponent of the feed solution. Transport through the membrane isinduced by maintaining the vapor pressure on the permeate side of themembrane lower than the vapor pressure of the feed mixture. The drivingforce for pervaporation is the difference in partial vapor pressure ofeach species across the membrane. One or more of the feed liquidcomponents pass through the membrane in vapor form. The non-permeatingfraction is removed as a liquid residue.

Gas separation is also a pressure-driven membrane process. In this case,a feed gas mixture at a certain pressure contacts one side of apermeselective membrane and a lower pressure is maintained on thepermeate side. The components of the mixture diffuse through themembrane under a potential gradient brought about the pressure dropacross the membrane. Vapor separation is a type of gas separationapplication in which the feed gas contains organic vapors that are to beremoved, typically, from air.

The optimum permselective membrane for use in any of these applicationscombines high selectivity with high flux. These two basic properties aredetermined by the membrane materials and the membrane thickness. As ageneral rule, high flux and high selectivity are mutually contradictoryproperties. Polymers with high selectivities for one component overanother tend to be relatively impermeable; highly permeable materials onthe other hand tend to be unselective. Thus the membrane-making industryhas engaged in an ongoing quest for membranes with improvedflux/selectivity performance.

One way to utilize highly selective materials and reduce the effect oflow permeability is to make the membrane extremely thin. One way tominimize membrane thickness is to prepare a composite membraneconsisting of a thin film coated onto a microporous support. Such amembrane is characterized on the basis of whether the coating or thesupport controls the separation properties. If the microporous supporthas a very high surface porosity, gas transport through the support willtake place by convective flow and/or Knudsen diffusion through thepores. On the other hand, if the microporous support has a surfaceporosity less than about 10⁻⁴, most of the gas transport will take placeby diffusion through the polymer phase, so that the support rather thanthe coating determines the separation properties. This is the case, forexample, with the membranes described in U.S. Pat. No. 4,230,463, toHenis and Tripodi, which are now sold commercially under the namePrism®. Membranes where the coating layer provides the separationproperties are described, for example, by Ward et al. In "Ultrathinsilicone rubber membranes for gas separation", J. Membrane Sci, 1, 99,1976, by Riley et al. in "Development of ultrathin membranes", Office ofSaline Water Report No. 386, PB #207036, and in U.S. Pat. No. 4,553,983to Baker. In addition, there are numerous other references in theliterature describing attempts to make ultrathin, defect-free membranes.Much of this work has been performed in the belief that the selectivityof the composite membrane will remain essentially the intrinsicselectivity of a thick film of the permselective material, but that thetransmembrane flux will increase as the permselective layer is madethinner. Therefore, it is customary to ascribe any loss of selectivityobserved with ultrathin membranes to defects in the permselective layer,through which unselective bulk transport of materials takes place.

SUMMARY OF THE INVENTION

The invention is a composite permselective membrane, optimized to givethe best combination of flux and selectivity performance. The inventionalso covers a process for designing such a membrane. The membranediffers from previous membranes available to the art in that it istailored by means of a model that shows that the membrane will possess aselectivity close to the intrinsic selectivity of the coating layer,only if the resistance to gas permeation of the composite structure iswithin the permselective coating layer. The model sets a limit on theminimum thickness for the permselective layer in relation to thepermeability of the support.

The invention recognizes that, contrary to the standard teachings in theart, it is not desirable to make the permselective coating layer as thinas possible. The invention also recognizes, again contrary to previousteachings, that drops in performance observed as the permselective layeris made thinner may not necessarily arise from defects in the layer, ashas been generally supposed, but rather may be inherent in thepermselective layer/support combination. The invention recognizes thatas the thickness of the permselective layer decreases, there comes apoint at which the selectivity of the composite membrane inevitablystarts to fall.

The present teachings also show that these effects are particularlynoticeable and significant where the selectivity for the more permeableover the less permeable component is large, such as occurs in separationof organic vapors from air, or in separation of some organic solventsfrom water, for example.

It is an object of the invention to provide composite separationmembranes optimized in terms of flux and selectivity performance.

It is an object of the invention to provide high performance membranesfor use in gas separation, vapor separation or pervaporationapplications.

It is an object of the invention to provide composite separationmembranes wherein the selectivity of the composite is at least 70% ofthe intrinsic selectivity of the permselective layer.

It is an object of the invention to provide a method for determining theminimum thickness of the permselective layer of a composite membrane foroptimum performance.

It is an object of the invention to provide a method for determining theminimum permeability of the support layer of a composite membrane foroptimum performance.

Other objects and advantages of the invention will be apparent from thedescription of the invention to those of ordinary skill in the art.

It is to be understood that the above summary and the following detaileddescription are intended to explain and illustrate the invention withoutrestricting its scope.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic cross-section of a composite membrane having amicroporous support layer and a very thin permselective coating layer.

FIG. 2 is a graph of the theoretical O₂ /N₂ selectivity of compositemembranes having a permselective layer of silicone rubber andmicroporous supports of varying normalized nitrogen fluxes.

FIG. 3 is a graph plotting the O₂ /N₂ selectivity performance ofcomposite membranes with silicone rubber permselective layers of varyingthicknesses.

FIG. 4 is a graph plotting the CO₂ /N₂ selectivity performance ofcomposite membranes with silicone rubber permselective layers of varyingthicknesses.

FIG. 5 is a graph plotting the C₂ Cl₄ /N₂ selectivity and C₂ Cl₄ fluxwith silicone rubber permselective layers of varying thicknesses.

DETAILED DESCRIPTION OF THE INVENTION

The term permselective as use herein refers to polymers, or membranesmade from those polymers, that exhibit selective permeation for at leastone component in a fluid mixture over the other components of themixture, enabling a measure of separation between the components to beachieved.

The term composite as used herein means comprising a support membraneand one or more coating layers.

The term intrinsic selectivity as used herein means the ratio of thepermeability coefficients of a polymer material for two fluids, asmeasured with a sample of the mixed fluids permeating through thickisotropic films of the polymer material.

The term vapor as used herein refers to organic compounds in the gaseousphase below their critical temperatures.

Good preselective membranes combine high selectivity with high flux.These two basic properties are determined by the membrane materials andthe membrane thickness. One way to minimize the membrane thickness is tomake a composite membrane consisting of a thin film coated on amicroporous support. Such membranes can be classified on the basis ofwhether the coating of the support controls the separation properties.If the microporous support has a high surface porosity, transportthrough the support will take place by convective flow or Knudsendiffusion through the pores. On the other hand, if the microporoussupport has a low surface porosity, typically about 10⁴ or below, mosttransport will be by diffusion through the polymer phase. This inventionis concerned only with composite membranes with high porosity supports.Previously it has been commonly assumed in the art that these compositemembranes will exhibit increasing flux as the thickness of thepermselective coating is reduced, and that the selectivity of thecomposite for two diffusing species will remain unchanged with changingmembrane thickness. (See, for example, A. S. Michaels, "Fundamentals ofMembrane Permeation", in Membrane Processes for Industry, Proceedings ofa Symposium sponsored by Southern Research Institute, 1966.) We havefound however that for these composite membranes the selectively is alsoa function of membrane thickness. This unexpected result is due to theresistance of the microporous support layer. Although the permselectivelayer may be intrinsically many times less permeable than the support,as the permselective coating becomes very thin, the resistance totransport in this layer is reduced to the point where the resistance ofthe support is no longer insiginficant, but can substantially affect theoverall performance of the membrane. We have found theoretically, andconfirmed experimentally, that for a given separation, support structureand permselective material, there is a limiting value at which thepermselective layer has the optimum thickness. At this permselectivelayer thickness, the membrane has the maximum flux attainable withoutcompromising selectivity. The selectivity of the composite is consideredto be unacceptably compromised when it falls to a value 70% or less ofthe intrinsic selectivity of a thick film of the permselective material.

A high-porosity-support composite membrane is shown in FIG. 1. Referringnow to this figure, composite membrane, 1, comprises a microporoussupport layer, 2, containing surface pores 3, through which fluidtransport in the support layer primarily takes place. The support layeris coated with a very thin permselective layer, 4, which determines theseparation properties of the membrane. A model that can be used topredict the separation behavior of the composite can be derived startingwith the standard expression for resistances in series, R=R₁ +R₂. For agas, A, the permeation rate through the membrane, J.sub.(A) can bewritten: ##EQU1## where Δp is the pressure difference across themembrane, l₁ is the thickness of the support layer, l₂ is thethicknesses of the permselective layer, P₁(A) is the permeabilitycoefficient of the support layer and P₂(A) is the permeabilitycoefficient of the permselective layer.

An equivalent expression can be written for a second gas, B. Theselectivity, α_(A/B) of the composite for gas A over gas B can beexpressed as the ratio of the permeation rates under equal pressuredriving forces:

    α.sub.A/B =J.sub.(A) /J(.sub.B)                      (2)

Combining equations 1 and 2 gives: ##EQU2##

It is apparent from this expression that the selectivity of the membraneis determined by both layers of the composite. Equations 2 and 3 arevalid for gas mixtures if the permeability coefficient of one gas is notaffected by the presence of the other.

When the resistance to gas permeation is essentially within thepermselective layer,

    l.sub.2 /P.sub.2(A) >>l.sub.1 /P.sub.1(A)                  (4a)

and

    l.sub.2 /P.sub.2(B) >>l.sub.1 /P.sub.1 (B)                 (4b)

so that Equation 3 reduces to: ##EQU3## which is the conventional beliefof the art. However, as will be shown, this simplification cannot bemade for high permeability, very thin membranes.

Equation 3 can be used to calculate the O₂ /N₂ selectivity of ahypothetical composite membrane having permselective membranes ofdifferent thicknesses coated onto microporous supports with varyingnormalized nitrogen fluxes. For example, the nitrogen permeabilitycoefficient of silicone rubber is about 270×10⁻³ cm³ (STP)cm/cm² ·s·cmHgand its O₂ /N₂ selectivity is 2.2. FIG. 2 shows the O₂ /N₂ selectivityof the composite membranes plotted against the thickness of the siliconerubber layer. Four different values for the normalized nitrogen flux,P₁(N2) /l₁ were used. It was assumed that the normalized oxygen fluxP₁(O2) /l₁ through the support is the same as the nitrogen flux. Thisassumption can be made because the gas flow occurs by Knudsen diffusionand Poiseuille flow, so essentially no selectivity for oxygen overnitrogen would be expected. As FIG. 2 shows, the O₂ /N₂ selectivity ofthe composite membrane increases with increasing silicone rubberthickness until the intrinsic selectivity of silicone rubber isapproached at some optimum thickness. The value of this optimumthickness depends on the normalized flux of the support. For example, toachieve a selectivity for the composite of 2.0 (90% of the intrinsicselectivity of silicone rubber) with a silicone rubber thickness lessthan 1 micron requires that the support should have a normalized flux ofnot less than about 5×10⁻³ cm³ (STP)cm.sup. ·s·cmHg. Thus our model canbe used to calculate the optimum permselective membrane thickness forany separation and support material. Conversely the model can be used totailor the normalized flux of the support used to carry a permselectivelayer of a particular thinness.

Equation 3 can also be used to calculate the minimum thickness of thepermselective layer when the selectivity of the composite is chosen tobear a specified relationship to the intrinsic selectivity of thepermselective material. Thus: ##EQU4## Hence: ##EQU5##

If the ratio of the desired selectivity to the intrinsic selectivity isK, this equation may also be written as: ##EQU6##

Another use for Equation 3 is to develop tables that can be used tocalculate the preferred permselective membrane thickness for any supportstructure. ##EQU7##

Because transport through the support layer is by pore flow, theresistance of the support membrane is approximately the same to allpermeating species, thus l₁ /P₁(A) =l₁ /P₁(B), and ##EQU8##

The intrinsic selectivity of the permselective material is theselecivity that would be achieved with thick films of the material andis therefore the ratio of the permeability coefficients in the materialP₂(A) /P₂(B). Dividing top and bottom by l₂ /P₂(A) therefore gives:##EQU9## where R is the ratio of the resistances of the permselectivelayer and the support, l₂ /P₂(A) /l₁ /P₁(A) to the more permeablespecies.

Therefore: ##EQU10##

This ratio becomes larger as the principal resistance to flow becomescentered in the permselective layer, i.e., l₂ /P₂(A) increases. Theresults of calculations for composite membranes having a permselectivelayer with an intrinsic selectivity of 2, 10 and 50 are listed in Table1.

                  TABLE 1                                                         ______________________________________                                                     Membrane Selectivity                                             Relative Resistance                                                                        Intrinsic Intrinsic   Intrinsic                                  to Flow of Component                                                                       Selectivity                                                                             Selectivity Selectivity                                A l.sub.2 /P.sub.2 (A)/l.sub.1 /P.sub.1 (A)                                                2         10          50                                         ______________________________________                                        2            1.67      7.0         33.7                                       4            1.80      8.2         40.2                                       6            1.83      8.7         43.0                                       8            1.89      9.0         44.6                                       10           1.91      9.2         45.5                                       12           1.92      9.3         46.2                                       20           1.95      9.6         47.7                                       100          1.99      9.9         49.5                                       ∞      2.00      10.0        50.0                                       ______________________________________                                    

If for a particular separation the desired selectivity is at least 9.0and the intrinsic selectivity is 10, then based on Table 1 the relativeresistance of the layers for the more rapidly permeating species must beat least 8.0. The resistance of the support layer material can bedetermined by measuring the pressure normalized gas flux through anuncoated support. This will yield a value for P₁(A) /l₁. A representivevalue for P₁(A) /l₁ measured in this way might be 1×10⁻³ cm³ (STP)/cm²·sec.·cmHg. Therefore the corresponding value of P₂(A) /l₂ is 1.25×10⁻⁴cm³ (STP)/cm² ·sec.·cmHg. If the permeability coefficient is, forexample, 1×10⁻⁸ cm³ (STP)cm/cm² ·sec·cmHg, then the optimum thickness ofthe permselective coating will be 0.8 μm. Thus to determine the optimumthickness for the permselective layer of a composite membrane accordingto the invention requires the following steps to be performed:

1. Determine the intrinsic selectivity and permeability of thepermselective material using thick films.

2. Determine the resistance to permeation of the support membrane bymeasuring the pressure normalized permeation rate through the uncoatedsupport.

3. Choose the desired selectivity for the composite.

4. Using Equation 3, or a table prepared as Table 1, calculate thepermselective layer thickness.

A similar series of steps can of course be carried out for apredetermined permselective membrane thickness to calculate the minimumpermissible permeability of the support membrane.

The above dicussion refers only to the permeation of gases throughcomposite membranes. However it should be appreciated that the samearguments and teachings would apply for the separation of vapors fromgases or from other vapors, or for the membrane process ofpervaporation. The invention is intended to embrace membraneoptimization methods and membranes for use in any of these applications.

Carrying out these optimizing steps, and then making a compositemembrane accordingly, will provide a membrane that can exhibit thehighest flux possible for that particular separation and combination ofmembrane materials without compromising the membrane selectivity. Thisoptimization is valuable wherever high-porosity-support compositemembranes are used. However the membranes and methods of the inventionare particularly valuable in situations where the intrinsic selectivityof the permselective material for one permeating species over another isvery high, typically 20 or above. This may clearly be seen by referringback to Table 1. Consider the first line of the table, where theresistance of the support, at half that of the permselective layer, issubstantial. If the intrinsic selectivity for the two permeating speciesis only 2, then the effect of the support will be to reduce theselectivity of the composite from a maximum possible value of 2 to anactual value of 1.67, a loss of performance of 16.5%. However if theintrinsic selectivity is 10, the selectivity of the composite is only 7,a loss of 30% in the selectivity performance. Likewise, when theintrinsic selectivity is 50, a loss of selectivity performance of almost38% occurs. If the intrinsic selectivity for the two components is 2, acomposite selectivity of 90% intrinsic selectivity can be reached whenthe ratio of the resistances is 4. If the intrinsic selectivity is 10,the resistance ratio must be 8 before the composite selectivity is 90%of the intrinsic value. If the intrinsic selectivity is 50, theresistance ratio must be at least 10 before the 90% level is reached.

Thus the invention provides a simple, but hitherto unrecognized,quantitative method to design composite membranes with thicknesses andpermeabilities tailored for very high performance. The invention alsoprovides membranes made in accordance with these teachings, and havingthe potential for high flux, combine with a selectivity close to theintrinsic selectivity of the permselective layer. Of course, membranesmade according to the invention will only exhibit this performance ifthe permselective layer is defect free. Pinholes or cracks in thepermselective coating will still permit bulk flow of gases or vaporsthrough the support, reducing the selectivity, but this effect will beable to be distinguished from the inherent limitations of the compositestructure. To achieve optimum performance, the operating parameters ofthe system incorporating the membrane, such as the pressure on thepermeate side, the transmembrane pressure ratio, and the stage cut,etc., must also be considered. However, once again, these effects are aseparate issue, and given that a viable system can be designed in termsof these parameters, the system will not be compromised by the inherentproperties of the membrane.

When the desired selectivity, the permeability of the support, and thepermselective membrane thickness have been chosen or calculated inaccordance with the model, the composite membrane must be made. Themembrane comprises a microporous support, onto which a very thinpermselective layer is coated. A preferred support membrane is anasymmetric Loeb-Sourirajan type membrane, which consists of a relativelyopen, porous substrate with a thin, dense, finely porous skin layer.Preferably the pores in the skin layer should be less than 1 micron indiameter, to enable it to be coated with a defect-free permselectivelayer. The substrate portion of the microporous layer can and shouldhave a porosity preferably not less than 20%, and more preferably about70% or above. The skin layer should be more finely porous, with a lowerporosity, to facilitate coating with the permselective material.Nevertheless, the porosity of the skin layer should preferably be notless than about 1%. Alternatively, simple isotropic microporous supportsmay be used. The resistance of the support layer compared with theresistance of the permselective layer should be such that the compositemembrane can possess a selectively not less than 70%, preferably notless than 80% and most preferably not less than 90%, of the intrinsicselectivity of the permselective material. To achieve a selectivity of90% the intrinsic value will require the support resistance to about0.25 that of the permselective layer if the intrinsic selectivity is 2,0.125 if the intrinsic selectivity is 10, and 0.1 if the intrinsicselectivity is 50, for example. To achieve a composite selectivity of80% of the intrinsic value will require the support resistance to beabout 0.5 that of the permselective layer if the intrinsic selectivityis 2, and about 0.25 if the intrinsic selectivity is greater than about10. To achieve a composite selectivity of 70% of the intrinsic valuewill require the support resistance to be about equal to that of thepermselective layer if the intrinsic selectivity is about 2, and about0.5 for higher intrinsic selectivities. Representative polymers whichmay be used for the support include polysulfone, polyimides, polyamides,polyetherimide, polyvinylidene fluoride, polyethylene, polypropylene,polyethersulfone or polytetrafluoroethylene. The material used for thesupport membrane should be capable for resisting the solvents used inapplying the permselective layer. If the polymer material used for thepermselective layer is soluble only in aggressive solvents, such astoluene, methylene chloride, or tetrahydrofuran, a solvent resistantsupport material, such as polyimide or polysulfone, is desirable.Suitable solvent-resistant polysulfone or polyimide membranes for use assupports may be purchased commercially. They are available asultrafiltration membranes, for example, the NTU® 4220 (crosslinkedpolyimide), or NTU®3050 (polysulfone) from Nitto Electric IndustrialCompany, Osaka, Japan. The thickness of the support membrane is notcritical, since its permeability is high compared to that of thepermselective layer. However the thickness would typically be in therange 100 to 300 microns.

Optionally, the support membrane may be reinforced by casting it on afabric web. The multilayer membrane then comprises the web, themicroporous membrane, and the ultrathin permselective membrane. The webmaterial may be, for example, a polyester such as Hollytex, availablefrom Eaton-Dikeman, Mt. Holly Springs, Pa. The permselective layer couldnot be cast directly on the fabric web, because it would penetrate theweb material, rather than forming an unbroken surface coating.

As an alternative to making the support membranes in flat sheet form,they may be spun as hollow fibers. The preparation of hollow fibers iswell known in the art, and is described, for instance, by B. Baum etal., "Hollow Fibers in Reverse Osmosis, Dialysis and Ultrafiltration",in Membrane Separation Processes, P. Meares, Ed., Elsevier, 1976.

The material used for the permselective layer will vary, depending onthe separation to be performed. Materials that could be used for thepermselective layer include, for example, silicone rubber,cholorosulfonated polyethylene, polysilicone-carbonate copolymers,fluoroelastomers, plasticized polyvinylchloride, polyurethane,polybutadiene, polystyrene-butadiene copolymers,styrene/butadiene/styrene block copolymers, polyacetylene, substitutedpolyacetylene, polyether/polyamide block copolymers, polymethylpentene,ethylcellulose, cellulose acetate and the like. The multilayer membranemay conveniently be formed in continuous rolls by casting and coating asdescribed, for example, in U.S. Pat. No. 4,553,983, incorporated hereinby reference. Typically, the membranes are prepared in two steps. Toform the microporous support membrane, a casting solution, consisting ofthe polymer dissolved in a water-miscible solvent, is doctored onto themoving web. The belt passes into a water bath which precipitates thepolymer to form the microporous membrane. The belt is then collected ona take-up roll, after which the membrane is washed to remove anyremaining solvent, dried to form the membrane, and wound up on a roll.In a second step, the microporous membrane from the feed roll passesthrough a dip-coating station, then a drying oven and is wound up on aproduct roll. The dip-coating tank contains a dilute solution of thepolymer and coats the traveling microporous membrane with a liquidlayer. After evaporation of the solvent, a very thin polymer film isleft on the membrane.

Alternatively, the permselective membrane may be cast by spreading athin film of the polymer solution on the surface of a water bath. Afterevaporation of the solvent, the permselective layer may be picked uponto the microporous support. This method is more difficult to practice,but may be useful if the desired support is attacked by the solvent usedto dissolve the permselective material.

The thickness of the permselective layer will be tailored in accordancewith the teachings of the invention, and will depend on the separationto be performed, the intrinsic selectivity of the permselective layer,and the permeability of the support. Typically for gas separation thethickness of the permselective layer may be 10 μm or less. For vaporseparation from air, or for pervaporation of some organic solvents fromwater, however, where the organic/non-organic selectivity is very high,it may be necessary to use a comparatively thick permselective layer,10-20 μm thick or even greater, if the selectivity is not to becompromised. The teachings of the invention are especially useful inthese circumstances, because the potential for previously unexplainedloss of selectivity is much greater.

The invention is now further illustrated by the following examples,which are intended to be illustrative of the invention, but are notintended to limit the scope or underlying principles of the invention inany way.

EXAMPLES Example 1 Composite membrane preparation

Asymmetric support membranes were made from polysulfone by theLoeb-Sourirajan precipitation method. A casting solution, consisting ofpolysulfone in a water-immiscible solvent, was doctored onto a movingbelt of polyester non-woven paper. The belt was then passed to acold-water bath which precipitated the polymer to form the supportmembrane. After the support has been washed and dried, the propertieswere measured in a commercial test cell (Millipore Corp., Bedford, MA)using membrane stamps of area 12.6 cm². Based on measurements with puregas streams, the support had a normalized nitrogen flux, P₁(N2) /l₁, of1.5×10⁻² cm³ (STP)/cm² ·s·cmHg, and an oxygen/nitrogen selectivity of0.95. The support membranes were coated with silicone rubber solutionsof varying thicknesses. After evaporation of the solvent, permselectivesilicone rubber layers of varying thicknesses were formed on the supportstructure.

Example 2 Gas separation oxygen/nitrogen

Gas permeation studies were carried out for composite membranes withmany different silicone rubber thicknesses. The permeation propertieswere measured in a test cell as above, using membrane stamps of area12.6 cm². The steady state permeation rates at 50 psig and 22° C. weremeasured with bubble flow meters. As before, the measurements were madewith pure gases.

The results are shown in FIG. 3. The solid line was calculated usingEquation 3. According to the experimental data, a silicone rubberthickness of 1 μm is necessary to obtain from the composite theintrinsic selectivity of silicone rubber for oxygen/nitrogen which isabout 22. This experimental minimum thickness is in agreement with themodel prediction. The deviations from the model at silicone rubberthickness less than 0.5 μm may be due to defects in the coating or toplugged pores in the support.

Example 3 Gas separation carbon dioxide/nitrogen

Experiments as in Examples 1 and 2 were carried out for carbon dioxideand nitrogen. The uncoated microporous support membrane had a normalizedcarbon dioxide flux, P₁(CO2) /l₁, of 1.4×10⁻² cm³ (STP)/cm² ·s·cmHg anda carbon dioxide/nitrogen selectivity of 0.93.

The carbon dioxide permeability coefficient of silicone rubber is3.1×10⁻⁷ cm³ (STP)cm/cm² ·s·cmHg, and the intrinsic selectivity forcarbon dioxide over nitrogen is 11.5.

The results of the permeation experiments for the composite membrane areshown in FIG. 4. The solid line was calculated using Equation 3. Aspredicted by the model, because silicone rubber is much more permeableto carbon dioxide than to nitrogen, the influence of the support is moresignificant. In this case, selectivities close to the intrinsicselectivity of silicone rubber were not obtained until the permselectivelayer was at least 2 μthick. That this effect was not due to defects inthe thinner membranes was checked by measuring the selectivity of thesame membranes with oxygen/nitrogen. The oxygen/nitrogen selectivity forall membrane above 0.5 μm thick was greater than 2, confirming that themembranes are essentially defect-free.

Example 4 Vapor separation

Experiments similar to those of Examples 1 and 2 were carried out forthe separation of tetrachloroethylene from nitrogen. In a preliminaryexperiment with a thick isotropic film of silicone rubber, the intrinsicselectivity for tetrachloroethylene over nitrogen was found to be 50.

In this case the properties of the composite membranes were tested inspiral-wound membrane modules with an effective membrane area of 1,500cm². All modules used in the experiments showed an oxygen/nitrogenselectivity of 2.0-2.2, and were thus essentially defect-free. Thesilicone rubber thicknesses used were 0.5, 4, 6.5 and 8 μm. Thesethicknesses were calculated from nitrogen permeation rates for theuncoated and the coated membranes. The performance of the modules withtetrachlorethylene/nitrogen mixtures is shown in FIG. 5. The solid lineswere calculated from the model, equations 1 and 3. As can be seen, therewas good experimental agreement with the model for both flux andselectivity. Although the membranes were defect-free, the intrinsicselectivity was never obtained, even when the permselective layer was 8μm thick. Because silicone rubber is very permeable totetrachloroethylene, the resistance of the support was comparable withthe resistance of the permselective layer.

The normalized nitrogen fluxes obtained from the gas mixture experimentswere the same as those from the pure gas measurements. It appeared,therefore, that no plasticization of the membranes by the organic vaporwas occurring.

We claim:
 1. A process for separating a first component, A, from a second component B, of a fluid mixture, comprising:providing a membrane having a feed side and a permeate side, said membrane comprising a composite of a microporous support layer having a thickness l₁ coated with a permselective layer, the permselective layer characterized in that it has an intrinsic selectivity α for a first component, A, over a second component, B, in a fluid mixture of at least 10, and a thickness l₂ given by: ##EQU11## where P₁(A) and P₁(B) are the permeabilities of the support layer to components A and B respectively, and where K is a constant having a value between 0.7 and 1; contacting said feed side with a fluid mixture comprising components A and B; withdrawing from said permeate side a permeate stream enriched in component A compared with said fluid mixture; withdrawing from said feed side a residue stream depleted in component A compared with said fluid mixture.
 2. The process of claim 1, wherein K is a constant having a value between 0.9 and
 1. 3. The process of claim 1, wherein said intrinsic selectivity is at least
 20. 4. The process of claim 1, wherein said microporous support layer is made from a polymer chosen from the group consisting of polysulfone, polyimides, polyamides, polyetherimide, polyvinylidene fluoride, polyethylene, polypropylene, polyetheresulfone and polytetrafluoroethylene.
 5. The process of claim 1, wherein said permselective layer is made from a polymer chosen from the group consisting of silicone rubber, chlorosulfonated polyethylene, polysilicone-carbonate copolymers, fluoroelastomers, plasticized polyvinylchloride, polyurethane, polybutadiene, polystyrene-butadiene copolymers, styrene/butadiene/styrene block copolymers, polyacetylene, substituted polyacetylene, polyether/polyamide block copolymers, polymethylpentene, ethylcellulose and cellulose acetates.
 6. The process of claim 1, wherein said first component is an organic vapor.
 7. The process of claim 1, wherein said first component is an organic liquid. 